Living Ring-Opening Metathesis–Polymerization Synthesis and Redox-Sensing Properties of Norbornene Polymers and Copolymers Containing Ferrocenyl and Tetraethylene Glycol Groups

Abstract

The controlled synthesis of monodisperse, redox-active metallopolymers and their redox properties and functions, including robust electrode derivatization and sensing, remains a challenge. Here a series of polynorbornene homopolymers and block copolymers containing side-chain amidoferrocenyl groups and tetraethylene glycol linkers were prepared via living ring-opening metathesis polymerization initiated by Grubbs’ third-generation catalyst (1). Their molecular weights were determined using MALDI-TOF mass spectra, size exclusion chromatography (SEC), end-group analysis, and the empirical Bard–Anson electrochemical equation. All polymerizations followed a living and controlled manner, and the number of amidoferrocenyl units varied from 5 to 332. These homopolymers and block copolymers were successfully used to prepare modified Pt electrodes that showed excellent stability. The modified Pt electrodes show excellent qualitative sensing of ATP2– anions, in particular those prepared with the block copolymers. The quantitative recognition and titration of [n-Bu4N]2[ATP] was carried out using the CH2Cl2 solution of the homopolymers, showing that two amidoferrocenyl groups of the homopolymers interacted with each ATP2– molecule. This stoichiometry led us to propose the H-bonding modes in the supramolecular polymeric network.

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…78) [357], various polymer chains [358], indole or purine groups [359], ferrocene groups (e.g. 75) [360,361], nucleic acid bases attached to an aminoethylglycine support [362], alkoxyquinoline groups (e.g. 77) [363], fluorescent groups and PEG groups (copolymer) [364]; polyoxometallates [365], dendriditically connected to a polylactate and a polystyrene system [366], and dendritic connection to anthraquinone moieties [367]; (19) bis(norbornenesuccinimide)s connected through a perylene ring [368]; (20) aza-Diels-Alder derived azanorbornenes (e.g.…”

Redox‐Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self‐Assembly of Pentamethylferricenium Polymer‐Embedded Ag, AgI, and Au Nanoparticles

“…[16] In the cyclic voltammogram( CV) measurements, the total number of electrons transferred in the oxidation wave for the polymer( n p )s hould be the same as the number of monomer units in the polymerb ecause only one electron from Fe II (PMF) to Fe III (PMFium) is transferred from each monomer unit to the anode.T hus this electron number n p can be estimated by using the Bard-Anson empirical equationt hat was previously derivedf or conventional polarography. [17] n p ¼ ði dp…”

“…In situ 1 HNMR spectroscopic analysis was used to detect the monomer conversions, which were calculated by comparing the intensities of the 1 HNMR signals of the olefinicp rotons between monomer 5 (d = 6.23 ppm) and polymers 6 (d = 5.49 and 5.72 ppm). Unlike in the case of the amidoferrocenyl-containing monomer,f or which ROMP polymerization requires ap rolonged reactiont ime, [16] ROMP of new PMF monomer 5 is completed in 10 min with nearly 100 % conversion whethert he feed molar ratio is high or low.T he fast polymerization rate is attributed to the presence of the C 5 Me 5 ligand that increases the solubility of the monomer in CH 2 Cl 2 .Unlike monomer 5,the obtained polymers are not soluble in acetone, acetonitrile, methanol (MeOH), or diethyl ether, but they are soluble in CH 2 Cl 2 ,c hloroform, tetrahydrofuran (THF), and strong polar solvents, such as dimethylformamide (DMF) andd imethylsulfoxide (DMSO).…”

The Redox Functions of Metallodendrimers

“…The model monophosphate anion H 2 PO 4 -as well as other oxo-anions had first been recognized in the 1990s [67][68][69][70][71]93], then further studies focused on the tetra-butyl ammonium salt of the ATP dianion itself [89,92]. Recently, binding ATP 2-sites were proposed based on the stoichiometry of redox recognition using ROMP-synthesized amido-Fc-containing norbornene polymers and co-polymers [96] (Fig 4).…”

“…Detailed hydrogen-bonding interactions between the phosphate groups of ATP 2-and the amido groups of an amido-Fc macromolecule[96] …”